Microlattice structures including flame retardant materials and compositions and methods for forming the same

ABSTRACT

A composition for forming a microlattice structure includes a photopolymerizable compound and a flame retardant material. A microlattice structure includes a plurality of struts interconnected at a plurality of nodes, the struts including: a copolymer including a reaction product of a photopolymerizable compound and a flame retardant material. A microlattice structure includes a plurality of struts interconnected at a plurality of nodes, the struts including: a polymer including a reaction product of a photopolymerizable compound; and a flame retardant material.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application claims priority to and the benefit of related U.S.Provisional Application Ser. No. 62/037,552, filed in the U.S. Patentand Trademark Office on Aug. 14, 2014, the entire content of which isincorporated herein by reference.

BACKGROUND

Flame retardant polymers are useful for various applications such asthose that have frequent and/or close contact with humans and that maybe exposed to open flames. For example, flame retardant polymers may beused in transportation applications, consumer goods, and the like.Previously, halogenated compounds (e.g., organohalogens) have been usedas flame retardants, but, because those halogenated compounds mayproduce halogen gas and/or halogen compounds that are environmentaltoxins and may corrode surrounding materials, there has been a push tomove away from such halogenated compounds. For example, the StockholmConvention on Persistent Organic Pollutants bans the use of 22organohalogens, many of which are used for flame retardant purposes.Additionally, the Restriction of Hazardous Substances (RoHS) Directiveof the European Union also bans the use of certain organohalogens due toenvironmental concerns.

While research has been conducted into non-halogen flame retardantcompounds, these compounds have processing constraints that lead to highloading levels of the compounds. Additionally, existing non-halogenflame retardant compounds are used in molding processes in which thearchitecture of the resultant part may be controlled, but thearchitecture of the chemistry within the part is not controlled.

SUMMARY

Aspects of embodiments of the present disclosure are directed towardflame retardant components included in a microlattice form factor, andcompositions and methods for forming the same.

Aspects of embodiments of the present disclosure are directed towardnon-halogen flame retardant materials that may be used at lower loadinglevels. Aspects of embodiments of the present disclosure are alsodirected toward methods for tailoring the architecture of a part as wellas the location of chemical compounds in the part.

According to an embodiment of the present disclosure, a composition forforming a microlattice structure, includes: a photopolymerizablecompound; and a flame retardant material.

The flame retardant material may include a photopolymerizable functionalgroup, and the flame retardant material and the photopolymerizablecompound may be adapted to copolymerize with each other.

According to another embodiment, a microlattice structure includes: aplurality of struts interconnected at a plurality of nodes, the strutsincluding: a copolymer including a reaction product ofphotopolymerizable compound and a flame retardant material.

According to another embodiment, a microlattice structure includes: aplurality of struts interconnected at a plurality of nodes, the strutsincluding: a polymer including a reaction product of aphotopolymerizable compound; and a flame retardant material.

According to another embodiment, a method of forming a microlatticestructure includes: exposing a composition including aphotopolymerizable compound and a flame retardant material to collimatedlight to form a precursor-microlattice structure; and curing theprecursor-microlattice structure to form the microlattice structure.

According to another embodiment, a method of forming a microlatticestructure includes: exposing a composition including aphotopolymerizable compound to collimated light to form aprecursor-microlattice structure; adding a flame retardant material tothe precursor-microlattice structure; and curing theprecursor-microlattice structure to form the microlattice structure.

The adding of the flame retardant material may include forming a coatingincluding the flame retardant material on the polymer.

The adding of the flame retardant material may be performed subsequentto the curing of the precursor-microlattice structure.

According to any of the above embodiments, the flame retardant materialof the coating may include a material selected from metals, ceramics,silicon, silicones, silica, nanoclay, nanoparticles, nanofibers, andmixtures thereof.

According to any of the above embodiments, the flame retardant materialincludes a photopolymerizable functional group and the exposing of thecomposition copolymerizes the flame retardant material with thephotopolymerizable compound.

According to any of the above embodiments, the exposing of thecomposition polymerizes the photopolymerizable compound to form apolymer.

According to any of the above embodiments, the curing of theprecursor-microlattice structure may form a chemical bond between theflame retardant material and the polymer.

According to any of the above embodiments, the chemical bond may beformed by a reaction of a first non-photopolymerizable functional groupof the polymer and a second non-photopolymerizable functional bonded tothe flame retardant material.

According to any of the above embodiments, the curing of theprecursor-microlattice structure may include thermal curing or moisturecuring.

The photopolymerizable functional group of the flame retardant materialaccording to any of the above embodiments may be selected from a thiolgroup, an alkenyl group, an alkynyl group, an acrylate group, an epoxygroup, and a methacrylate group.

The flame retardant material according to any of the above embodimentsmay be selected from a phosphate, a phosphonate, a phosphinate, and amixture thereof.

The flame retardant material according to any of the above embodimentsmay be included in the composition in an amount of 1 to 33 wt % based onthe total weight of the composition.

The flame retardant material according to any of the above embodimentsmay include particles including a material selected from aluminatrihydrate, ammonium polyphosphate, red phosphorous, an organicphosphinate, melamine polyphosphate, borates, expandable graphite, aphosphorous based oligomer, and a mixture thereof.

According to any of the above embodiments, the photopolymerizablecompound may include a photopolymerizable functional group and a firstnon-photopolymerizable functional group, a second non-photopolymerizablefunctional group may be bonded to the flame retardant material, and thefirst non-photopolymerizable functional group and the secondnon-photopolymerizable functional group may be adapted to react witheach other upon curing.

According to any of the above embodiments, the firstnon-photopolymerizable functional group may be selected from anisocyanate group, a hydroxyl group, an amine group, a carboxylic acidgroup, an epoxy group, a silyl ether, and a combination thereof, and thesecond non-photopolymerizable functional group may be selected from anisocyanate group, a hydroxyl group, an amine group, a carboxylic acidgroup, an epoxy group, and a combination thereof.

According to any of the above embodiments, the photopolymerizablecompound may include a first compound including an unsaturatedcarbon-carbon bond and a second compound including a terminal thiolgroup.

According to any of the above embodiments, the first compound includingthe unsaturated carbon-carbon bond may be selected from the groupconsisting of ethylene, substituted olefins, 1,3-dienes, styrene,α-methyl styrene, vinyl esters, acrylates, methacrylates,acrylonitriles, acrylamides, N-vinyl carbazoles, N-vinyl pyrrolidone,and mixtures thereof.

According to any of the above embodiments, the second compound includingthe terminal thiol group may be selected from the group consisting ofpentaerythritol-tetra-3-mercaptopropionate, trimethylolpropanetris(3-mercaptopropionate), 1,6-hexanedithiol, trimethylolpropanetris(2-mercaptoacetate), ethoxylated trimethylolpropanetris(3-mercaptopropionate), glycol di-3-mercaptopropionate, and mixturesthereof.

According to any of the above embodiments, the first compound includingthe unsaturated carbon-carbon bond may be included in the composition inan amount of 10 to 99 wt/a %, and the second compound including theterminal thiol group may be included in the composition in an amount of10 to 99 wt %, based on the total weight of the composition.

According to any of the embodiments above, the polymer may at leastpartially surround the flame retardant material.

According to any of the embodiments above, the struts include a coatingincluding the flame retardant material on the polymer.

According to any of the above embodiments, the flame retardant materialmay be attached to the polymer by a chemical bond.

According to any of the above embodiments, the chemical bond may beformed by a reaction of a first non-photopolymerizable functional groupof the photopolymerizable compound and a second non-photopolymerizablefunctional group bonded to the flame retardant material.

According to any of the above embodiments, the firstnon-photopolymerizable functional group may be selected from anisocyanate group, a hydroxyl group, an amine group, a carboxylic acidgroup, an epoxy group, a silyl ether, and a combination thereof, and thesecond non-photopolymerizable functional group may be selected from anisocyanate group, a hydroxyl group, an amine group, a carboxylic acidgroup, an epoxy group, and a combination thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, together with the specification, illustrateembodiments of the present disclosure, and, together with thedescription, serve to explain the principles of the present invention.

FIG. 1 is a schematic cross-sectional diagram illustrating an embodimentof a system for forming a microlattice structure.

FIGS. 2 and 3 are schematic top views of embodiments of aperturepatterns for forming microlattice structures.

FIGS. 4 and 5 are schematic perspective views of respective portions ofembodiments of microlattice structures.

FIG. 6 is a schematic diagram illustrating embodiments of microlatticestructures.

FIG. 7 is a schematic diagram illustrating embodiments of compounds forforming microlattice structures.

FIGS. 8-16 are schematic diagrams illustrating embodiments of reactionsfor forming microlattice structures.

FIGS. 17 and 18 are schematic diagrams illustrating embodiments ofreactions for forming microlattice structures.

DETAILED DESCRIPTION

In the following detailed description, only certain embodiments of thepresent disclosure are shown and described, by way of illustration. Asthose skilled in the art would recognize, the invention may be embodiedin many different forms and should not be construed as being limited tothe embodiments set forth herein. Accordingly, the drawings anddescription are to be regarded as illustrative in nature, and notrestrictive.

Embodiments of the present disclosure relate to a microlattice structureincluding a flame retardant material (e.g., a non-halogen flameretardant material), and compositions and methods for forming the same.As used herein, a flame retardant material is any material that reduces,suppresses, or delays the formation of flames (or fire) to prevent orreduce the formation or spread of fire. The flame retardant material mayinclude, for example, a particle, a precursor utilized to form a polymer(e.g., a copolymer, prepolymer or oligomer), a portion of the polymer(e.g., the portion of the polymer that includes the reacted precursor),or a coating.

Accordingly, the flame retardant material may be included in and/or on,struts (e.g., polymer waveguides) of the microlattice structure.Including the flame retardant material in and/or on the struts of themicrolattice structure provides architectural control for tailoring thechemistry of the microlattice structure inside, and at the surface of,the struts. For example, the struts of the microlattice structure may beformed by copolymerizing the flame retardant material with anothercompound (e.g., a photopolymerizable compound). In such embodiments, thestruts of the microlattice include (or are defined by) a copolymerincluding the flame retardant material (e.g., a copolymerized reactionproduct of the flame retardant material and the other compound).

Additionally, or alternatively, the flame retardant material may bephysically trapped (or entrained) in the struts of the microlatticestructure. For example, the flame retardant material may be encased in apolymer that is included in (or defines) the struts. In someembodiments, the polymer may be formed (e.g., polymerized) to at leastpartially surround the flame retardant material by forming (e.g.,polymerizing) a compound (e.g., a photopolymerizable compound) in thepresence of the flame retardant material, thereby at least partiallysurrounding the flame retardant material (or trapping the particles inthe polymer).

Additionally, or alternatively, the flame retardant material may beincorporated into the microlattice structure through orthogonalchemistry (e.g., by way of orthogonal chemical reactions). Theorthogonal chemistry may utilize, for example, a first reaction, and asecond reaction (e.g., an orthogonal reaction) to form the microlatticestructure. The first reaction (e.g., a photopolymerization reaction suchas a UV-initiated, free-radical or ionic reaction) forms aprecursor-microlattice structure, and the second reaction, which isdifferent from (e.g., orthogonal to) the first reaction, forms themicrolattice structure from the precursor-microlattice structure. Forexample, the second reaction may be a photopolymerization reaction thatis different from the first reaction (e.g., is initiated at a wavelengththat is different than that of the first reaction), a thermal curingreaction, or a moisture curing reaction (e.g., a reaction of isocyanateterminated monomers, oligomers, prepolymers, or polymers that areadapted to cure in the presence of ambient water).

Accordingly, in some embodiments, the flame retardant material includesa functional group that reacts during the second reaction, but does notreact during the first reaction that forms the precursor-microlatticestructure. The first reaction forms “green” struts of theprecursor-microlattice structure, and the flame retardant material maybe bonded to the “green” struts of the precursor-microlattice by way ofthe second reaction, which may also cross-link theprecursor-microlattice structure to form the microlattice structure. Theprecursor-microlattice may be formed in the presence of the flameretardant material, and/or the flame retardant material may be added tothe precursor-microlattice structure after the first reaction isperformed. In embodiments of the orthogonal chemistry process, the“green” struts of the microlattice structure may be formed from acompound (e.g., a photopolymerizable compound) including aphotopolymerizable functional group and an orthogonal functional group(e.g., a functional group that reacts during the second reaction, butdoes not react during the first reaction). Utilizing monomers,oligomers, prepolymers and/or polymers having a first functional groupthat reacts during the first reaction and a second functional group thatreacts during the second reaction provides a cross-linked structure (ora higher cross-linked structure), which may prevent or reduce melting ofthe microlattice structure, and subsequent dripping, when themicrolattice structure is exposed to a flame.

Additionally, or alternatively, the flame retardant material may be onthe struts of the microlattice structure (e.g., as a coating). Thecoating may be formed on the precursor-microlattice structure followedby curing of the precursor-microlattice structure, and/or the coatingmay be formed on the cured microlattice structure. The coating may beformed by any suitable process, such as dip coating, painting, spraying,melting, sintering, peening, electroplating a metallic coating includingflame retardant fillers, and/or charging a coating and usingelectrostatics to attract the coating to the microlattice structure orprecursor-microlattice structure.

The flame retardant material may provide flame retardancy in anysuitable manner. For example, the flame retardant portion may limit thefuel supply (e.g., oxygen and/or other readily combustible material suchas organic material) for a flame by releasing water or other inertsubstances, increase char formation to create a noncombustible layer(e.g., a protective layer), and/or reduce temperature through anendothermic reaction. In some embodiments, the flame retardant materialincludes an organophosphorus and/or nitrogen based compound, but theflame retardant material is not limited thereto. Non-limiting examplesof organophosphorus and nitrogen based compounds include melamine,cyanurate, phosphate esters, and phosphonic acids.

The microlattice structure may be formed using any suitable equipmentand processes available in the art. For example, the microlatticestructure may be formed using equipment and processes described in U.S.Pat. No. 7,382,959, titled “Optically Oriented Three-Dimensional PolymerMicrostructures,” the entire content of which is incorporated herein byreference.

FIG. 1 is a schematic cross-sectional diagram illustrating a system 100for forming a microlattice structure according to an embodiment of thepresent disclosure. As shown in FIG. 1, the microlattice structure 110may be formed using a single collimated beam (e.g., a beam ofultraviolet (UV) light) or a plurality of independently collimated beamsthrough a patterning apparatus 104 (e.g., a mask) located at a side of areservoir 102 (e.g., a molding chamber) having (or containing) acomposition 108 including components (e.g., a photopolymerizablecompound and, optionally, a flame retardant material) that initiate apolymerization (or copolymerization) process upon contact with the beamor beams emitted from a light source 120. The patterning apparatus 104may include a plurality of apertures 106 (e.g., gaps or openings). Eachof the apertures 106 may have a given (or set) shape and dimensiondefining (e.g., substantially matching) a cross-sectional geometry of astrut 112 (e.g., a self-propagating optical polymer waveguide) of themicrolattice structure 110. The microlattice structure 110 may have athree-dimensional (3D) structure defined by the struts 112.

In an embodiment, the mask 104 may be on a transparent substrate (ortransparent plate) that forms a side (e.g., a bottom side) of thereservoir 102. In another embodiment, the mask 104 may include thetransparent substrate. For example, portions of the transparentsubstrate may be made to be opaque (or substantially opaque) while otherportions of the transparent substrate may remain transparent (orsubstantially transparent) to allow the beam or beams to be transmittedthrough the other portions of the transparent substrate.

The apertures 106 may be arranged in a pattern, such as a rectangularpattern (or square pattern) as shown in FIG. 2 and/or in a hexagonalpattern as shown in FIG. 3. A distance between apertures 106 in the mask104, and the number of struts 112 formed from the apertures 106 willdetermine the open volume fraction (e.g., open space) of themicrolattice structure. By controlling the arrangement of the apertures106, as well as the other features of the system of FIG. 1, themicrolattice structure may be designed for a given application. Some ofthe design parameters for forming the microlattice structure include: 1)the angle and pattern of the struts with respect to one another, 2) therelative density of the resulting cellular structure (or the open volumefraction), and 3) the cross-sectional shape and dimensions of thestruts.

As can be seen in FIG. 1, a thickness (or height) of the microlatticestructure 110 may be controlled by filling the reservoir 102 with thecomposition 108 to a set height. Once the beam or beams are applied, thestruts 112 (e.g., intersecting struts) grow from a surface of the mask104 (or a surface of the transparent substrate) and culminate orterminate at a free (e.g., upper) surface of the composition 108 in thereservoir 102 to form the struts 112 (e.g., grown waveguides) of themicrolattice structure 110. In some embodiments, the struts 112 (e.g.,the intersecting polymer waveguides) polymerize or copolymerize to formthe precursor-microlattice structure or microlattice structure. Thestruts 112 may independently have a diameter (e.g., thickness) of about10 μm to about 10 mm, and may intersect at nodes that may be distancedapart from one another by a distance of about 2 to about 20 times thenode diameter.

According to an embodiment, a precursor-microlattice structure may beformed and/or shaped using the beam or beams, and then further cured(e.g., post-cured or surface cured) by any suitable curing meansavailable in the art, for example, photocuring, thermal curing, and/ormoisture curing. The beam or beams may initiate a reaction (e.g., thefirst or second reactions) by way of a photoinitiator. Any suitablephotoinitiatior available in the art may be utilized. For example, themicrolattice structure or precursor-microlattice structure may be formedusing a plurality of photoiniators and/or a plurality of light sources,for example, as described in U.S. patent application Ser. No.14/255,623, filed on Apr. 17, 2014 and titled “Method For CuringStructures Using A Dual Photoinitiator System and Structure Made UsingThe Same,” the entire contents of which are incorporated by referenceherein. The cured microlattice structure or precursor-microlatticestructure may have a 3D ordered open-cellular microstructure.

For example, in the embodiments shown in FIGS. 4 and 5, the struts ofthe microlattice structure 110 include first truss elements 114, secondtruss elements 116, and third truss elements 118. The first trusselements 114 are defined by first self-propagating polymer waveguidesand extend along a first direction A. The second truss elements 116 aredefined by second self-propagating polymer waveguides and extend along asecond direction B. The third truss elements 118 are defined by thirdself-propagating polymer waveguides and extend along a third directionC. The truss elements 114, 116, and 118 interpenetrate each other atnodes 122 to form a continuous material having a three-dimensionalmicrostructure order and having a plurality of three-dimensional orderedpores (or spaces) defined by (or between) the truss elements 114, 116,118 and the nodes 122. In some embodiments, the continuous material iscontinuously formed such that it lacks any interior boundaries, e.g.,boundaries within the interpenetrating portions of truss elements 114,116, and 118. In some embodiments, each node 122 of the microlatticestructure 110 is formed of the continuous material. As should berecognized by a person of ordinary skill in the art to which thisdisclosure pertains, alterations and changes in the describedmicrolattice structure and precursor-microlattice structure and themethod of forming the same can be practiced without meaningfullydeparting from the principles, spirit, and scope of this disclosure, asdescribed herein.

For example, embodiments of the microlattice structure are not limitedto a single UV curing reaction, as that may limit the end groupchemistry of monomers utilized to form the microlattice structure andmay preclude many chemistries that may improve the structural andchemical properties of the microlattice structure. As such, themicrolattice structure is not limited to any particular end groupchemistry of the monomers utilized to form the microlattice structure.For example, the microlattice structure may be formed utilizing a widevariety of chemical precursors, thereby increasing the range ofproperties that the final microlattice structure may possess anddecreasing the cost of the chemical precursors by allowing for theutilization of monomers used in other structural polymer fields. Some ofthose polymers, such as urethanes and epoxies, have been developed morethan acrylates and thiol-enes leading to the development of more costeffective monomers having improved structural capabilities, ambientcondition reactivity, and chemical functionality such as flameretardance, chemical resistance, etc. By utilizing orthogonal reactivefunctionality to form the microlattice structure, a far greater range offinal microlattice chemistries and, therefore, properties may beaccessed. One of the benefits provided by aspects of embodiments of thecopolymer method of the present disclosure is that we may now architectand form 3D cellular structures using chemistries that otherwise cannotbe directed (e.g., chemistries that are otherwise agnostic towards thedirection of reaction). According to embodiments of the presentdisclosure, flame retardant materials (e.g., fire retardant materials)may now be incorporated into the microlattice structure through non-UVpolymerizable chemistries.

FIG. 6 is a schematic diagram illustrating certain ways in which theform factor of the microlattice structure 110 can be utilized as amicrolattice structure including the flame retardant material. Forexample, in FIG. 6, a microlattice structure 130 includes a coatingincluding a flame retardant material, a microlattice structure 132includes a flame retardant material (e.g., a filler, such as particlesor a polymer of flame retardant material) embedded or physicallyentrained or trapped in struts, and a microlattice structure 134includes a copolymer including a flame retardant material.

FIG. 7 is a schematic diagram showing non-limiting schematicrepresentations of compounds that may be used to form theprecursor-microlattice structure or the microlattice structure accordingto embodiments of the present disclosure. For example, as shown in FIG.7 a flame retardant material 202, a photopolymerizable compound 204, aphotopolymerizable compound 206, and/or a flame retardant material 208may be combined (e.g., polymerized, copolymerized, and/or cross-linked)to form the precursor-microlattice structure or the microlatticestructure. The compounds illustrated in FIG. 7 can be combined in avariety of suitable ways to form the precursor-microlattice structure orthe microlattice structure. The flame retardant material 202, thephotopolymerizable compound 204, the photopolymerizable compound 206,and the flame retardant material 208 may each independently be amonomer, comonomer, oligomer, prepolymer, polymer, copolymer or amixture thereof.

The flame retardant material 202 may include a phosphate, a phosphonate,and/or a phosphinate, and a suitable reactive group or groups may bebonded to the phosphate, the phosphonate, and/or the phosphinate. Forexample, the flame retardant material 202 may include the phosphate(e.g., an organic phosphate):

the phosphonate (e.g., an organic phosponate):

and/or the phosphinate (e.g., an organic phosphinate):

In the foregoing chemical formulae, R₁, R₂, and R₃ may eachindependently be any suitable functional group capable of reactingduring the first or second reactions described herein.

For example, as can be seen in FIG. 7, a photopolymerizable functionalgroup 210 may be bonded to the flame retardant material 202. Anon-limiting, commercially available example of the flame retardantmaterial 202 includes bis[2-(methacryloyloxy)ethyl]phosphate. Thephotopolymerizable compound 204 and the photopolymerizable compound 206may also each include the photopolymerizable functional group 210. Thephotopolymerizable functional group 210 may react during the firstreaction. For example, the photopolymerizable functional group 210 ofthe flame retardant material 202, the photopolymerizable compound 204,and the photopolymerizable compound 206 may each independently be afunctional group that reacts during a photopolymerization reaction(e.g., a photopolymerization reaction, such as a UV-initiated, freeradical or ionic reaction) to form a polymer or copolymer. Thephotopolymerizable functional group may be any suitable functional groupthat is susceptible to a UV initiator (e.g., free radical UV initiators,cationic UV initiators, and the like). Non-limiting examples of thephotopolymerizable functional group 210 include thiols, alkenes,alkynes, acrylates, epoxies, and/or methacrylates. Thephotopolymerizable compound 204 and the photopolymerizable compound 206may include any suitable backbone available in the art.

In certain embodiments, the photopolymerizable compound 204 and/orphotopolymerizable compound 206 include a first compound including anunsaturated carbon-carbon bond and a second compound including aterminal thiol group. The unsaturated carbon-carbon bond of the firstcompound may include a carbon-carbon double bond and/or a carbon-carbontriple bond. For example, the first compound including the unsaturatedcarbon-carbon bond may include ethylene, substituted olefins,1,3-dienes, styrene, α-methyl styrene, vinyl esters, acrylates,methacrylates, acrylonitriles, acrylamides, N-vinyl carbazoles, N-vinylpyrrolidone, and mixtures thereof. The second compound including theterminal thiol group may includepentaerythritol-tetra-3-mercaptopropionate, trimethylolpropanetris(3-mercaptopropionate), 1,6-hexanedithiol, trimethylolpropanetris(2-mercaptoacetate), ethoxylated trimethylolpropanetris(3-mercaptopropionate), glycol di-3-mercaptopropionate, and mixturesthereof. The first compound including the unsaturated carbon-carbon bondmay be included in a composition for forming the microlattice structurein an amount of 10 to 99 wt %. The second compound including theterminal thiol group may be included in the composition in an amount of10 to 99 wt %, based on the total weight of the composition.

In addition to the reactive functional group 210, the photopolymerizablecompound 206 may also include a reactive functional group 212 (e.g., afirst non-photopolymerizable functional group). A reactive functionalgroup 214 (e.g., a second non-photopolymerizable functional group) maybe bonded to the flame retardant material. The reactive functional group212 and the reactive functional group 214 may be non-reactive during thefirst reaction (e.g., a photopolymerization reaction, such as aUV-initiated, free radical or ionic reaction), but the reactivefunctional group 212 may react with the reactive functional group 214during the second reaction (e.g., a photopolymerization reaction at adifferent wavelength, a thermal curing reaction, or a moisture curingreaction). Non-limiting examples of the reactive functional group 212(e.g., the first non-photopolymerizable functional group) include anisocyanate group, a hydroxyl group, an amine group, a carboxylic acidgroup, an epoxy group, and/or a silyl ether (a silyl ether group).Non-limiting examples of the reactive functional group 214 (e.g., thesecond non-photopolymerizable functional group) include an isocyanategroup, a hydroxyl group, an amine group, a carboxylic acid group, and/oran epoxy group. For example, the hydroxyl group of the reactivefunctional group 212 and/or the reactive functional group 214 may beincluded in any suitable alcohol available in the art.

FIGS. 8-16 are schematic diagrams illustrating reactions of the flameretardant material 202, the photopolymerizable compound 204, thephotopolymerizable compound 206, and/or the flame retardant material 208that may be utilized to form the microlattice structure and/orprecursor-microlattice structure according to embodiments of the presentdisclosure. For example, as shown in FIG. 8, the flame retardantmaterial 202 and the photopolymerizable compound 204 may be reacted(e.g., copolymerized) in the first reaction (e.g., a photopolymerizationreaction, such as a UV-initiated, free radical or ionic reaction) toform a copolymer 230. The copolymer 230 may be included in, or maydefine, the struts of the microlattice structure. In FIGS. 8-16, thebrackets indicate repeating structures, but the polymers and copolymersshown in FIGS. 8-16 are not limited to the patterns shown as thepolymers and copolymers may include any suitable arrangement ofcomponents, such as those found in alternating copolymers, periodiccopolymers, statistical copolymers, block copolymers, and/or graftcopolymers.

As shown in FIG. 9, the photopolymerizable compound 206 may be reacted(e.g., polymerized in the first reaction (e.g., a photopolymerizationreaction, such as a UV-initiated, free radical or ionic reaction) toform a polymer 232. The polymer 232 may be included in, or may define,the struts of the precursor microlattice structure. As shown in FIG. 10,the polymer 232 may be reacted (e.g., copolymerized, cross-linked, orcured) with the flame retardant material 208 through the second reaction(e.g., a photopolymerization reaction at a different wavelength, athermal curing reaction, or a moisture curing reaction) to form acopolymer 234. The copolymer 234 may be included in, or may define, thestruts of the microlattice structure.

As shown in FIG. 11, the photopolymerizable compound 204 and thephotopolymerizable compound 206 may be reacted (e.g., copolymerized) inthe first reaction (e.g., a photopolymerization reaction, such as aUV-initiated, free radical or ionic reaction) to form a copolymer 236.The copolymer 236 may be included in, or may define, the struts of theprecursor microlattice structure. As shown in FIG. 12, the copolymer 236may be reacted (e.g., copolymerized, cross-linked, or cured) with theflame retardant material 208 through the second reaction (e.g., aphotopolymerization reaction at a different wavelength, a thermal curingreaction, or a moisture curing reaction) to form a copolymer 238. Thecopolymer 238 may be included in, or may define, the struts of themicrolattice structure.

As shown in FIG. 13, the flame retardant material 202 and thephotopolymerizable compound 206 may be reacted (e.g., copolymerized) inthe first reaction (e.g., a photopolymerization reaction, such as aUV-initiated, free radical or ionic reaction) to form a copolymer 240.The copolymer 240 may be included in, or may define, the struts of theprecursor-microlattice structure. As shown in FIG. 14, the copolymer 240may be reacted (e.g., copolymerized, cross-linked, or cured) with theflame retardant material 208 through the second reaction (e.g., aphotopolymerization reaction at a different wavelength, a thermal curingreaction, or a moisture curing reaction) to form a copolymer 242. Thecopolymer 242 may be included in, or may define, the struts of themicrolattice structure.

As shown in FIG. 15, the flame retardant material 202, thephotopolymerizable compound 204, and the photopolymerizable compound 206may be reacted (e.g., copolymerized) in the first reaction (e.g., aphotopolymerization reaction, such as a UV-initiated, free radical orionic reaction) to form a copolymer 244. The copolymer 244 may beincluded in, or may define, the struts of the precursor-microlatticestructure. As shown in FIG. 15, the copolymer 244 may be reacted (e.g.,copolymerized, cross-linked, or cured) with the flame retardant material208 through the second reaction (e.g., a photopolymerization reaction ata different wavelength, a thermal curing reaction, or a moisture curingreaction) to form a copolymer 246. The copolymer 246 may be included in,or may define, the struts of the microlattice structure.

Additionally, or alternatively, the microlattice structure may include aflame retardant material that is not chemically bonded to a polymer thatdefines the struts of the microlattice structure. For example, thestruts of the microlattice structure may include, or be defined by, apolymer formed from any of the above-described photopolymerizablecompounds (e.g., the polymer may include a reaction product of any ofthe above-described photopolymerizable compounds), and the polymer mayat least partially surround the flame retardant material. For example,the flame retardant material may be embedded or physically entrained ortrapped in the polymer. The flame retardant material may include apolymer (e.g., a secondary polymeric phase) that is different from thepolymer that defines the struts, and/or the flame retardant material mayinclude particles (e.g., fillers).

For example, flame retardant solids in particle form may be introducedinto a composition including any of the photopolymerizable compoundsdescribed herein in order to reduce flammability and/or reduce theevolution of toxic smoke during combustion of the microlatticestructure. Particles such as, but not limited to, alumina trihydrate,ammonium polyphosphate, red phosphorous, organic phosphinate, melaminepolyphosphate, borates, and expandable graphite may be introduced anddispersed in the composition to achieve suitable or desired combustionbehavior.

The particles may be opaque and/or scatter light. Thus, if the particlesare included in the composition at too high of a concentration, theparticles will excessively scatter or reflect the UV light and therebyimpede or reduce the formation of the microlattice structure. Suitableconcentrations of the particles will be affected by the height (ordepth) of the microlattice structure being formed as the height of themicrolattice structure affects the depth to which the UV light shouldpenetrate. The concentration of the particles in the composition may be1 to 33 wt %, for example, 4 to 10 wt %, based on the total weight ofthe composition. In one embodiment, particles including ammonium weredispersed in a composition including a photomonomer resin, andconcentrations of the particles as high as 4 wt %, based on the totalweight of the composition, were achievable without significant orsubstantial degradation of the ability to form a 12.7 mm thickmicrolattice structure.

The particles may be added to the composition in any suitable manneravailable in the art. For example, the particles may be introduced in adry powder form, in a suspension of photomonomer (e.g., a suspension ofthe photopolymerizable compound), or in a solvent that is laterevaporated. Non-limiting examples of the solvent include acetone,toluene, isopropanol, and mixtures thereof. The particles may bedispersed in the composition via mechanical mixing. The particles mayalso be surface treated to promote adhesion with the resin (e.g., thepolymer, or to prevent or reduce agglomeration of particles in thecomposition (or suspension).

The secondary polymeric phase that is not bonded to or crosslinked withthe photomonomer resin (e.g., the photopolymerizable compound or polymeror copolymer formed from the photopolymerizable compound) may also beincluded in the microlattice structure as an additive or filler. Thesecondary polymeric phase may be transparent to UV light, and therefore,the secondary polymeric phase may be included in the composition at aconcentration higher than that of the particles. Including the secondarypolymeric phase in the composition may result in a refractive indexmismatch, which may limit or reduce the depth to which UV light maypenetrate the composition. Thus, suitable concentrations of thesecondary polymeric phase will be affected by the height (or depth) ofthe microlattice structure being formed as the height of themicrolattice structure affects the depth to which the UV light shouldpenetrate. For example, the secondary polymeric phase may be included inthe composition in an amount of 1 to 33 wt % based on the total weightof the composition.

In one embodiment, a secondary polymeric phase including a phosphorousbased oligomer was dissolved in a solvent and introduced into thephotomonomer resin (the composition) to impart flame retardancy.Alternatively, or additionally, such an oligomer may be introducedsuspended in an uncured liquid polymer/oligomer carrier which may becured in place after UV curing of the photomonomer (thephotopolymerizable compound), the liquid polymer/oligomer and flameretardant oligomer thus forming a secondary flame retardant phase in thefinal microlattice structure. The secondary polymeric phase may beintroduced and dispersed in the same manner as described for flameretardant particles.

FIG. 17 is a schematic diagram illustrating embodiments of methods offorming a microlattice structure. As shown in FIG. 17, according to oneembodiment, a composition 300 includes an unreacted flame retardantmaterial 302. The flame retardant material 302 may include any of theflame retardant materials described herein (e.g., the flame retardantmaterials 202 and/or 208, flame retardant particles, and/or the flameretardant polymer). The composition 300 may further include any of thephotopolymerizable compounds described herein (e.g., thephotopolymerizable compounds 204 and/or 206). The composition 300 mayfurther include any suitable components available in the art, such asphotoinitiators, stabilizers, inhibitors, and the like. Further,according to any of the embodiments disclosed herein, an inhibitorand/or an initiator may include a flame retardant material. By addingphosphorus groups to the inhibitor and/or initiator an amount of theflame retardant material in the microlattice structure may be increasedwith relatively lower reduction in the thermal and/or mechanicalproperties of the microlattice structure since a majority of thebackbone forming monomers may be added to the composition. Thecomposition 300 is utilized to form a precursor-microlattice structure304 via the first reaction (e.g., UV-initiated photopolymerization).

In the first reaction, the unreacted flame retardant material 302 reactswith the photopolymerizable compound and/or other unreacted flameretardant material to form struts of the precursor-microlatticestructure 304. Thus, the precursor-microlattice structure 304 includesthe reacted flame retardant material 302. The precursor-microlatticestructure 304 may then be reacted by way of a second reaction (e.g., aphotopolymerization reaction at a wavelength different than that of thefirst reaction, a thermal curing reaction, and/or a moisture curingreaction) to form a microlattice structure 308 including the reactedflame retardant material 306. A polymer of the precursor-microlatticestructure 304 may fully crosslink during the second reaction.

As also shown in FIG. 17, a microlattice structure may be formed from acomposition 310, for example, by way of a dual cure process (e.g., a gelprocess). The composition 310 includes an unreacted flame retardantmaterial 312. The unreacted flame retardant material 312 may include anyof the flame retardant materials described herein (e.g., the flameretardant materials 202 and/or 208, flame retardant particles, and/orthe flame retardant polymer). The composition 310 may further includeany of the photopolymerizable compounds described herein (e.g., thephotopolymerizable compounds 204 and/or 206). The composition 310 mayfurther include any suitable components available in the art, such asphotoinitiators, stabilizers, inhibitors, and the like. The composition310 is utilized to form a precursor-microlattice structure 314 via thefirst reaction (e.g., UV-initiated photopolymerization).

The precursor-microlattice structure 314 includes the unreacted flameretardant material 302. The unreacted flame retardant material 312 maybe on and/or embedded or physically entrained or trapped in a polymer ofstruts of the precursor-microlattice structure 314. Theprecursor-microlattice structure 314 may then be reacted by way of asecond reaction (e.g., a photopolymerization reaction at a wavelengthdifferent than that of the first reaction, a thermal curing reaction,and/or a moisture curing reaction) to form a microlattice structure 316including a reacted flame retardant material 318. For example, theunreacted flame retardant material 312 may react (e.g., crosslink) withthe polymer of the struts of the precursor-microlattice structure 314 toform struts of the microlattice structure 318 that include the reactedflame retardant material 316. The polymer of the precursor-microlatticestructure 314 may fully crosslink during the second reaction.

As also shown in FIG. 17, a microlattice structure may be formed from acomposition 320, for example, by way of a soak process. The composition320 includes at least one of the photopolymerizable compounds describedherein (e.g., the photopolymerizable compounds 204 and/or 206), but thecomposition 320 does not include the flame retardant material. Thecomposition 320 may further include any suitable components available inthe art, such as photoinitiators, stabilizers, inhibitors, and the like.The composition 320 is utilized to form a precursor-microlatticestructure 322 via the first reaction (e.g., UV-initiatedphotopolymerization).

An unreacted flame retardant material 326 may then be added to thecomposition 320, and/or the precursor-microlattice structure 322 may beadded to a composition 324 including the unreacted flame retardantmaterial 326. The unreacted flame retardant material 326 may include anyof the flame retardant materials described herein (e.g., the flameretardant materials 202 and/or 208, flame retardant particles, and/orthe flame retardant polymer). The unreacted flame retardant material 326may be on and/or swelled into a polymer of struts of theprecursor-microlattice structure 322. The precursor-microlatticestructure 322 and unreacted flame retardant material 326 may then bereacted by way of a second reaction (e.g., a photopolymerizationreaction at a wavelength different than that of the first reaction, athermal curing reaction, and/or a moisture curing reaction) to form amicrolattice structure 328 including a reacted flame retardant material330. For example, the unreacted flame retardant material 326 may react(e.g., crosslink) with the polymer of the struts of theprecursor-microlattice structure 322 to form struts of the microlatticestructure 328 that include the reacted flame retardant material 330. Theunreacted flame retardant material 326 may be selectively at a surfaceof the struts of the precursor-microlattice structure 328, or theunreacted flame retardant material 326 may be incorporated substantiallythroughout the struts of the precursor-microlattice structure 324, andthen reacted.

FIG. 18 is a schematic diagram illustrating embodiments of methods offorming a microlattice structure including a coating. For example, asshown in FIG. 18, a composition 400 is reacted (e.g., cured) by thefirst reaction to form a precursor-microlattice structure 402. Theprecursor-microlattice structure 402 may then be reacted (e.g., cured)by the second reaction to form a microlattice structure 404. A coatingincluding a flame retardant material is then applied to or formed on themicrolattice structure 404 to form a coated microlattice structure 406.In some embodiments, the coating including the flame retardant materialis applied to or formed on the precursor-microlattice structure 402, andthe coated precursor-microlattice structure is reacted (e.g., cured) bythe second reaction to form the coated microlattice structure 406. Thecoating may be applied by any suitable method available in the artincluding, but not limited to, dip coating, painting, spraying, melting,sintering, peening, electroplating a metallic coating including flameretardant fillers, and/or charging a coating and utilizingelectrostatics to attract two materials. Applying or forming the coatingon the precursor-microlattice structure allows available bonding sitesof the precursor-microlattice structure to assist with forming chemicalbonds between the coating and the precursor-microlattice structure. Themicrolattice structure or precursor-microlattice structure may beroughened before the coating is applied or formed to provide suitableadhesion.

Non-limiting examples of noncombustible materials that may be includedin the coating include: metals, ceramics, silicon, silicones, silica,nanoclay, or other nanoparticles or nanofibers. The mechanisms forceasing, inhibiting or reducing combustion may be substantially the sameas described for the other flame retardant materials (e.g., creating aprotective char layer, decreasing the temperature, outputting inertgases, and/or simply not providing any combustibles). Optical clarity ofthe composition is not as much of a consideration for the coating asmicrolattice fabrication process (e.g., UV initiation) is separate.Thus, the coating may utilize solid particles (e.g., inorganic fillers)including, but not limited to, red phosphorus, aluminum trihydroxide(ATH), ammonium polyphosphate (APP). A flowable adhesive as a carriermay be utilized to help with applying and/or forming the coating. Thecoating provides the flame retardant material at surfaces of themicrolattice structure and, thus, the total volume percentage of theflame retardant material may be decreased because the additives areconcentrated at the surface and the impact on the mechanical propertiesof the microlattice structure may be reduced.

According to embodiments of the present disclosure, reactions that areotherwise agnostic towards direction may be architected during thecuring process by way of orthogonal chemistry. Examples of suchreactions include the isocyanate-alcohol or amine reactions that formpolyurethanes and polyureas, respectively. These condensationpolymerization reactions would otherwise occur substantially uniformlythroughout a reaction vessel, so long as sufficient reactants andcatalysts are available. On the other hand, orthogonal chemistry allowsfor the reaction of orthogonal functional groups independently of eachother. Orthogonal functional groups are functional groups that do notengage in similar or identical reactions or that exhibit substantialdifferences in their respective chemical reactivities (e.g., by way ofprotecting groups that may subsequently be removed to allow theprotecting group to react, for example, as a result of photocuring,thermal curing, and/or moisture curing).

On the other hand, according to embodiments of the present disclosure,the microlattice structure may be formed by way of a first reaction anda second reaction, and the polyurethane and/or polyurea may be formed tobe included in the struts (e.g., by way of copolymerization) and/or maybe grafted onto a surface of the struts to form an ordered structureincluding polyurethane and/or polyurea. Since the micro-latticestructure may be formed utilizing a UV-initiated, free-radical or ionicreaction, embodiments of the copolymer reaction enable two orthogonalreactions: a first reaction utilizing UV initiation, and a secondreaction utilizing another mechanism. Embodiments of this disclosureenable the incorporation of multiple functionalities into a structuralmicrolattice that are incompatible with a UV initiated curing mechanism.Thus, embodiments of flame retardant material may be incorporatedthrough non-UV polymerizable chemistries.

Embodiments of the disclosed subject matter may be utilized in anysuitable application as a flame retardant material. For example,embodiments of the microlattice structures may be used as structuralpolymers where flame retardant properties are beneficial, such astransportation applications, consumer goods, and/or the like, but thepresent disclosure is not limited thereto. Embodiments of themicrolattice structures may be utilized in lightweight structuralmaterials, conformable core structures, acoustic damping, hook and loopattachments; compliant structures; optics for sub-micron waveguideformation; single body casting/net shape manufacturing; alternate shapesfor waveguide members (3D honeycomb); functionally graded structures;heat exchanger/insulator structures; 3D battery/fuel cell structures;thermal switch structures; catalyst support structures;filtration/separation structures; wicking materials/moisture controlstructures; directional optical coupler/flexible display structures;distributed lighting structures; electrical interconnects; sensorsupports with high surface areas; biological growth templates; flexiblebody/reactive armors; stealth coatings; high friction/high wearsurfaces; waveguides for other energy sources; flame retardant foams;etc.

Examples of transportation applications of the disclosed subject matterinclude vehicle interiors (e.g., interiors of spacecraft, aircraft,automobiles, subway cars, trains, buses, and the like), battery trays,engine trays, casings near fuel sources, and/or the like, but thepresent disclosure is not limited thereto. Examples of consumer goodapplications of the disclosed subject matter include casings forelectronic equipment (e.g., casings for batteries or power supplies inappliances or other electronic), furniture, insulation, and/or the like,but the present disclosure is not limited thereto.

The embodiments described herein may each be used singly or incombination to provide an article having a flame retardant property. Forexample, some of the flame retardant materials may have a high affinitywater, which may be detrimental if the flame retardant material absorbsexcess moisture from the environment, thereby reducing the flameretardancy of the flame retardant material prior to a flame incident. Assuch, synergy may be achieved by combining one or more of theembodiments described herein. For example, including flame retardantmaterials that have a relatively lower affinity for moisture, orutilizing higher cross-linked systems may reduce the effects ofenvironmental moisture on the flame retardancy.

Further, the flame retardant particles (or fillers) may affect theoptical properties of the composition for forming the microlatticestructure and, thus, in some embodiments, the amount of the flameretardant particles in the composition may be controlled. In someembodiments, the amount of flame retardant material included in thecopolymer may be controlled to reduce an effect of the flame retardantmaterial on thermal and/or mechanical properties of the copolymer.Accordingly, in some embodiments, the microlattice structure may includea copolymer including the flame retardant material and the copolymer mayat least partially surround flame retardant particles to reduce theeffect of the flame retardant particles on the optical properties of thecomposition and to reduce the effect of the flame retardant material onthe thermal and/or mechanical properties of the copolymer, while stillproviding suitable flame retardancy. Thus, a microlattice structureaccording to embodiments of the present disclosure may not be limited toa flame retardant additive, copolymer, or coating, but, on the contrary,may include one or more of the flame retardant additive, copolymer, orcoating.

As used herein, the terms polymer and copolymer are used broadly andinclude oligomers and prepolymers. Additionally, polymers and copolymersdescribed herein may be formed from monomers, comonomers, oligomers, andprepolymers. As used herein, expressions of the singular also encompassthe plural and vice versa. For example, a description of a microlatticestructure may also encompass a plurality of microlattice structures andvice versa. Additionally, any numerical range recited herein is intendedto include all sub-ranges of the same numerical precision subsumedwithin the recited range. For example, a range of “1.0 to 10.0” isintended to include all subranges between (and including) the recitedminimum value of 1.0 and the recited maximum value of 10.0, that is,having a minimum value equal to or greater than 1.0 and a maximum valueequal to or less than 10.0, such as, for example, 2.4 to 7.6. Anymaximum numerical limitation recited herein is intended to include alllower numerical limitations subsumed therein and any minimum numericallimitation recited in this specification is intended to include allhigher numerical limitations subsumed therein.

Also, in the context of the present application, when a first element isreferred to as being “on” a second element, it can be directly on thesecond element or be indirectly on the second element with one or moreintervening elements interposed therebetween. Like reference numeralsdesignate like elements throughout the specification.

Expressions such as “at least one of,” when preceding a list ofelements, modify the entire list of elements and do not modify theindividual elements of the list. Further, the use of “may” whendescribing embodiments of the present invention refers to “one or moreembodiments of the present invention.”

As used herein, the terms “use,” “using,” and “used” may be consideredsynonymous with the terms “utilize,” “utilizing.” and “utilized,”respectively. As used herein, the term “substantially,” “about,” andsimilar terms are used as terms of approximation and not as terms ofdegree, and are intended to account for the inherent deviations inmeasured or calculated values that would be recognized by those ofordinary skill in the art. Moreover, the acts described above may beperformed in the order described or in any other suitable sequence.Additionally, the methods described above are not limited to the tasksdescribed. Instead, for each embodiment, one or more of the tasksdescribed above may be absent and/or additional tasks may be performed.

While the present invention has been described in connection withcertain embodiments, it is to be understood that the invention is notlimited to the disclosed embodiments, but, on the contrary, is intendedto cover various modifications and equivalent arrangements includedwithin the spirit and scope of the appended claims, and equivalentsthereof.

What is claimed is:
 1. A composition for forming a microlatticestructure, comprising: a photopolymerizable compound comprising a firstcompound and a second compound, the first compound comprising anunsaturated carbon-carbon bond and the second compound comprising aterminal thiol group; and a flame retardant material.
 2. The compositionof claim 1, wherein the first compound comprising the unsaturatedcarbon-carbon bond is selected from the group consisting of ethylene,substituted olefins, 1,3-dienes, styrene, α-methyl styrene, vinylesters, acrylates, methacrylates, acrylonitriles, acrylamides, N-vinylcarbazoles, N-vinyl pyrrolidone, and mixtures thereof.
 3. Thecomposition of claim 1, wherein the second compound comprising theterminal thiol group is selected from the group consisting ofpentaerythritol-tetra-3-mercaptopropionate, trimethylolpropanetris(3-mercaptopropionate), 1,6-hexanedithiol, trimethylolpropanetris(2-mercaptoacetate), ethoxylated trimethylolpropanetris(3-mercaptopropionate), glycol di-3-mercaptopropionate, and mixturesthereof.
 4. The composition of claim 1, wherein the first compoundcomprising the unsaturated carbon-carbon bond is included in thecomposition in an amount of 10 to 99 wt %, and the second compoundcomprising the terminal thiol group is included in the composition in anamount of 10 to 99 wt %, based on the total weight of the composition.5. The composition of claim 1, wherein a photopolymerizable functionalgroup is bonded to the flame retardant material, and thephotopolymerizable functional group of the flame retardant material andthe photopolymerizable compound are adapted to react with each other toform a copolymer.
 6. The composition of claim 5, wherein thephotopolymerizable functional group of the flame retardant material isselected from a thiol group, an alkenyl group, an alkynyl group, anacrylate group, an epoxy group, and a methacrylate group.
 7. Thecomposition of claim 5, wherein the flame retardant material is selectedfrom a phosphate, a phosphonate, a phosphinate, and a mixture thereof.8. The composition of claim 1, wherein the flame retardant material isincluded in the composition in an amount of 1 to 33 wt % based on thetotal weight of the composition.
 9. The composition of claim 1, whereinthe flame retardant material comprises particles comprising a materialselected from alumina trihydrate, ammonium polyphosphate, redphosphorous, an organic phosphinate, melamine polyphosphate, borates,expandable graphite, a phosphorous based oligomer, and a mixturethereof.
 10. The composition of claim 1, wherein the photopolymerizablecompound comprises a photopolymerizable functional group and a firstnon-photopolymerizable functional group, wherein a secondnon-photopolymerizable functional group is bonded to the flame retardantmaterial, and wherein the first non-photopolymerizable functional groupand the second non-photopolymerizable functional group are adapted toreact with each other.
 11. The composition of claim 10, wherein thefirst non-photopolymerizable functional group is selected from anisocyanate group, a hydroxyl group, an amine group, a carboxylic acidgroup, an epoxy group, a silyl ether, and a combination thereof, andwherein the second non-photopolymerizable functional group is selectedfrom an isocyanate group, a hydroxyl group, an amine group, a carboxylicacid group, an epoxy group, and a combination thereof.
 12. A orderedmicrolattice structure comprising: a plurality of struts interconnectedat a plurality of nodes, the struts comprising: a copolymer comprising areaction product of a photopolymerizable compound and a flame retardantmaterial.
 13. The microlattice structure of claim 12, wherein thephotopolymerizable compound comprises a first compound comprising anunsaturated carbon-carbon bond and a second compound comprising aterminal thiol group.
 14. The microlattice structure of claim 13,wherein the first compound comprising the unsaturated carbon-carbon bondis selected from the group consisting of ethylene, substituted olefins,1,3-dienes, styrene, α-methyl styrene, vinyl esters, acrylates,methacrylates, acrylonitriles, acrylamides, N-vinyl carbazoles, N-vinylpyrrolidone, and mixtures thereof.
 15. The microlattice structure ofclaim 13, wherein the second compound comprising the terminal thiolgroup is selected from the group consisting ofpentaerythritol-tetra-3-mercaptopropionate, trimethylolpropanetris(3-mercaptopropionate), 1,6-hexanedithiol, trimethylolpropanetris(2-mercaptoacetate), ethoxylated trimethylolpropanetris(3-mercaptopropionate), glycol di-3-mercaptopropionate, and mixturesthereof.
 16. The microlattice structure of claim 12, wherein aphotopolymerizable functional group is bonded to the flame retardantmaterial, and the photopolymerizable functional group of the flameretardant material is selected from a thiol group, an alkenyl group, analkynyl group, an acrylate group, an epoxy group, and a methacrylategroup.
 17. The microlattice structure of claim 12, wherein the flameretardant material is selected from a phosphate, a phosphonate, aphosphinate, and a mixture thereof.
 18. A ordered microlattice structurecomprising: a plurality of struts interconnected at a plurality ofnodes, the struts comprising: a polymer comprising a reaction product ofa photopolymerizable compound; and a flame retardant material.
 19. Themicrolattice structure of claim 18, wherein the polymer at leastpartially surrounds the flame retardant material.
 20. The microlatticeof claim 19, wherein the flame retardant material comprises particlescomprising a material selected from alumina trihydrate, ammoniumpolyphosphate, red phosphorous, an organic phosphinate, melaminepolyphosphate, borates, expandable graphite, a phosphorous basedoligomer, and a mixture thereof.
 21. The microlattice structure of claim18, wherein the struts comprise a coating comprising the flame retardantmaterial on the polymer.
 22. The microlattice structure of claim 18,wherein the flame retardant material is attached to the polymer by achemical bond.
 23. The microlattice structure of claim 22, wherein thechemical bond is formed by a reaction of a first non-photopolymerizablefunctional group of the photopolymerizable compound and a secondnon-photopolymerizable functional group bonded to the flame retardantmaterial.
 24. The microlattice structure of claim 23, wherein the firstnon-photopolymerizable functional group is selected from an isocyanategroup, a hydroxyl group, an amine group, a carboxylic acid group, anepoxy group, a silyl ether, and a combination thereof, and wherein thesecond non-photopolymerizable functional group is selected from anisocyanate group, a hydroxyl group, an amine group, a carboxylic acidgroup, an epoxy group, and a combination thereof.
 25. A method offorming a microlattice structure, the method comprising: exposing acomposition comprising a photopolymerizable compound and a flameretardant material to collimated light to form a precursor-microlatticestructure; and curing the precursor-microlattice structure to form themicrolattice structure.
 26. The method of claim 25, wherein aphotopolymerizable functional group is bonded to the flame retardantmaterial and the exposing of the composition copolymerizes the flameretardant material with the photopolymerizable compound.
 27. The methodof claim 26, wherein the photopolymerizable functional group of theflame retardant material is selected from a thiol group, an alkenylgroup, an alkynyl group, an acrylate group, an epoxy group, and amethacrylate group.
 28. The method of claim 26, wherein the flameretardant material is selected from a phosphate, a phosphonate, aphosphinate, and a mixture thereof.
 29. The method of claim 25, whereinthe flame retardant material is included in the composition in an amountof 1 to 33 wt % based on the total weight of the composition.
 30. Themethod of claim 25, wherein the exposing of the composition polymerizesthe photopolymerizable compound to form a polymer.
 31. The method ofclaim 30, wherein the flame retardant material comprises particlescomprising a material selected from alumina trihydrate, ammoniumpolyphosphate, red phosphorous, an organic phosphinate, melaminepolyphosphate, borates, expandable graphite, a phosphorous basedoligomer, and a mixture thereof, and wherein the polymer at leastpartially surrounds the particles.
 32. The method of claim 30, whereinthe curing of the precursor-microlattice structure forms a chemical bondbetween the flame retardant material and the polymer.
 33. The method ofclaim 32, wherein the chemical bond is formed by a reaction of a firstnon-photopolymerizable functional group of the polymer and a secondnon-photopolymerizable functional group bonded to the flame retardantmaterial.
 34. The method of claim 33, the first non-photopolymerizablefunctional group is selected from an isocyanate group, a hydroxyl group,an amine group, a carboxylic acid group, an epoxy group, a silyl ether,and a combination thereof, and wherein the second non-photopolymerizablefunctional group is selected from an isocyanate group, a hydroxyl group,an amine group, a carboxylic acid group, an epoxy group, and acombination thereof.
 35. The method of claim 33, wherein the curing ofthe precursor-microlattice structure comprises thermal curing ormoisture curing.
 36. A method of forming a microlattice structure, themethod comprising: exposing a composition comprising aphotopolymerizable compound to collimated light to form aprecursor-microlattice structure; adding a flame retardant material tothe precursor-microlattice structure; and curing theprecursor-microlattice structure to form the microlattice structure. 37.The method of claim 36, wherein the exposing of the compositionpolymerizes the photopolymerizable compound to form a polymer.
 38. Themethod of claim 37, wherein the adding of the flame retardant materialcomprises forming a coating comprising the flame retardant material onthe polymer.
 39. The method of claim 38, wherein the flame retardantmaterial of the coating comprises a material selected from metals,ceramics, silicon, silicones, silica, nanoclay, nanoparticles,nanofibers, and mixtures thereof.
 40. The method of claim 38, whereinthe adding of the flame retardant material is performed subsequent tothe curing of the precursor-microlattice structure.
 41. The method ofclaim 37, wherein the curing of the precursor-microlattice structureforms a chemical bond between the flame retardant material and thepolymer.
 42. The method of claim 41, wherein the chemical bond is formedby a reaction of a first non-photopolymerizable functional group of thepolymer and a second non-photopolymerizable functional group bonded tothe flame retardant material.
 43. The method of claim 42, the firstnon-photopolymerizable functional group is selected from an isocyanategroup, a hydroxyl group, an amine group, a carboxylic acid group, anepoxy group, a silyl ether, and a combination thereof, and wherein thesecond non-photopolymerizable functional group is selected from anisocyanate group, a hydroxyl group, an amine group, a carboxylic acidgroup, an epoxy group, and a combination thereof.
 44. The method ofclaim 42, wherein the curing of the precursor-microlattice structurecomprises thermal curing or moisture curing.